EP3430002B1 - Furansäureherstellungsverfahren - Google Patents

Furansäureherstellungsverfahren Download PDF

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Publication number
EP3430002B1
EP3430002B1 EP17710561.6A EP17710561A EP3430002B1 EP 3430002 B1 EP3430002 B1 EP 3430002B1 EP 17710561 A EP17710561 A EP 17710561A EP 3430002 B1 EP3430002 B1 EP 3430002B1
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Prior art keywords
furfural
process according
catalyst
oxidation
gold
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French (fr)
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EP3430002B8 (de
EP3430002A1 (de
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Francesco SANTARELLI
Robert WOJCIESZAK
Sébastien PAUL
Franck Dumeignil
Fabrizio Cavani
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Centre National de la Recherche Scientifique CNRS
Ecole Centrale de Lille
Universite de Lille
Universita di Bologna
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Centre National de la Recherche Scientifique CNRS
Ecole Centrale de Lille
Universita di Bologna
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties

Definitions

  • the present invention relates to a heterogeneous catalytic process for the preparation of furoic acid or one of its derivatives from furfural or one of its derivatives in the liquid phase.
  • Furoic acid also called 2-furoic acid, or furan-2-carboxylic acid, or alpha-furoic acid
  • 2-furoic acid also called 2-furoic acid, or furan-2-carboxylic acid, or alpha-furoic acid
  • furoic acid in the field of food, can be used as a preservative in the stages of pasteurization and sterilization, thus acting as a bactericidal and fungicidal agent. It can also be used as a flavoring agent.
  • this compound can be useful in the preparation of nylons.
  • Furoic acid also makes it possible to obtain esters of furoic acid and is frequently used as an intermediate in the chemical, pharmaceutical and agrochemical industries.
  • 2,5-furan dicarboxylic acid also known by the abbreviation FDCA
  • FDCA 2,5-furan dicarboxylic acid
  • Furoic acid can also be easily hydrogenated to tetrahydrofuroic acid, a very important intermediate in the pharmaceutical industry.
  • a conventional approach consists in oxidizing the furfuraldehyde in an alkaline medium in the presence of a catalyst. It should be noted that the use of an alkaline medium is necessary to achieve good catalytic performance in the oxidation reaction.
  • furoic acid is synthesized using AgO / Cu 2 O catalysts.
  • such a process suffers from the need for a high catalyst load, from the use of a dilute medium, and the existence of side reactions.
  • Furfural not only undergoes oxidation to furoic acid, but also side reactions resulting from the cleavage of the furan ring.
  • the catalyst must be periodically regenerated insofar as the Cu 2 O phase is not stable.
  • furoic acid Another approach to the chemical synthesis of furoic acid requires a preliminary Canizzaro reaction from furfuralin in an aqueous NaOH solution to obtain furfuryl alcohol and sodium 2-furanecarboxylate. The next step is the reaction of sodium 2-furanecarboxylate with sulfuric acid to obtain furoic acid.
  • the major drawback of this process is the limitation of the theoretical yield of furoic acid to 50% and the generation of a large amount of sodium hydrogen sulphate which must be removed from the reaction mixture.
  • WO2013096998 describes a process for producing a mixture of 2,4-furanedicarboxylic acid and 2,5-furanedicarboxylic acid in alkali metal.
  • Furoic acid can also be synthesized via biotechnological processes ( Perez et al., African Journal of Biotechnology, 2009, 8 (10), 2279-2282 ; Eilers et al., Planta, 1970, 94, 253-264 ; Luna et al., Rev. Mex.
  • fungi such as those of the species Neurospora crassa and Neurospora ascospora
  • yeasts such as Saccharomyces cerevisiae
  • bacteria such as those of the genus Acetobacter, Bacillus, Zooglea, Nocardia and Pseudomonas.
  • furoic acid can be prepared by oxidation of furfuraldehyde using a biocatalytic microbial preparation with Nocardia corallina B-276 ( Perez et al., African Journal of Biotechnology, 2009, 8 (10), 2279-2282 ).
  • Nocardia corallina B-276 Perez et al., African Journal of Biotechnology, 2009, 8 (10), 2279-2282 .
  • the oxidation with Nocardia corallina has been considered as interesting insofar as the use of most of the other microorganisms leads to the production of two oxidation products, namely the corresponding acid and alcohol.
  • no destruction of the furan cycle is observed.
  • drawbacks remain.
  • one of the objectives of the invention is to provide a heterogeneous catalysis process, making it possible to directly produce furoic acid or one of its free derivatives in water (and not in the form of an alkali salt) with very high efficiency.
  • Another objective of the invention is to provide a heterogeneous catalysis process which does not require working in an alkaline medium and therefore makes it possible to overcome the phenomenon of degradation of the catalyst support and the loss of metal residues generally encountered under alkaline conditions. .
  • Another objective of the present invention is to provide a heterogeneous catalysis process making it possible to obtain high yields of furoic acid and advantageously in a reduced reaction time.
  • Another objective of the present invention is to provide a process using a heterogeneous catalyst which can be easily recycled without requiring prior treatment.
  • a non-alkaline aqueous medium denotes a medium of non-alkaline pH, that is to say of pH less than 8 and preferably at most equal to 6.
  • this aqueous medium is devoid of organic solvent.
  • this aqueous medium consists of water as solvent medium.
  • a C 1 -C 6 alkyl group denotes an alkyl group comprising from 1 to 6 carbon atoms.
  • Such an alkyl group can be linear or branched and can be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl.
  • the process according to the invention makes it possible to obtain a furoic acid derivative of formula (I) in which at most two of the groups R 1 , R 2 , R 3 and R 4 represent a group - COOH.
  • the process according to the invention can lead to the production of a furoic acid derivative of formula (I) in which R 1 and R 2 , or R 1 and R 3 , or R 1 and R 4 , or R 2 and R 3 each represent a -COOH group and the remaining two groups represent, independently of each other, a hydrogen atom or a C 1 -C 6 alkyl group linear or branched, preferably a hydrogen atom.
  • the process according to the invention makes it possible to obtain a furoic acid derivative of formula (I) in which R 1 and R 4 each represent a -COOH group, and R 2 and R 3 represent a hydrogen atom. It is then the 2,5-furan dicarboxylic acid.
  • the process according to the invention makes it possible to obtain a furoic acid derivative of formula (I) in which only one of the groups R 1 , R 2 , R 3 and R 4 is a group -COOH, and the remaining three groups are, independently of each other, a hydrogen atom or a linear or branched C 1 -C 6 alkyl group.
  • the process according to the invention makes it possible to obtain a furoic acid derivative of formula (I) in which R 4 is a -COOH group, and R 1 , R 2 , and R 3 represent a hydrogen atom. This is then the furoic acid itself.
  • the method according to the invention is particularly advantageous in several respects.
  • the conversion of a furfural derivative of formula (II) into its oxidation derivative of formula (I), in this case furoic acid for furfural, is carried out in a single step in the presence of gaseous oxygen in presence of a supported gold-based catalyst.
  • the process according to the invention takes advantage of very effective catalytic formulations which are reactive in a non-basic medium.
  • This advantage allows direct access to the acid form of the compound of formula (II) and not to its alkali salt.
  • the subsequent step of converting this salt into an acid is therefore no longer required and the production of a large quantity of salts which may or may not be valuable is avoided.
  • the gold contents in the solutions after 4 hours and 15.5 hours of reaction were measured by ICP-OES (measurements by ICP optical emission spectrometry, induced plasma analysis). They were found to be below the detection limit of the analyzer indicating that passage of gold from solid catalyst to solution (a phenomenon known as leaching) does not occur for catalysts suitable for use. the present invention.
  • step (b) is carried out with stirring and under a pressure of the order of 15 bars (ie 15.10 5 Pa) by heating the assembly to a temperature between 70 ° C and 150 ° C, from preferably between 90 ° C to 120 ° C, even more preferably from 110 ° C.
  • reaction time (or duration) is adjusted to obtain a yield of furoic acid derivative of formula (I) at least equal to 80%.
  • This reaction time can advantageously be only 1 to 4 hours.
  • the catalyst used is gold supported on zirconium dioxide.
  • the catalyst used is gold supported on hydrotalcite.
  • the process according to the invention makes it possible to obtain a furoic acid derivative of formula (I) and more particularly furoic acid with a conversion, a yield, high selectivity and carbon footprint.
  • conversion rate denotes the ratio of the number of moles of furfural derivative of formula (II) having reacted divided by the number of moles of furfural derivative of formula (II ) initially introduced.
  • selectivity means the ratio of the number of moles of furoic acid derivative of formula (I) obtained at the end of the reaction divided by the number of moles of furfural derivative of formula (II) which has reacted.
  • yield means the ratio of the number of moles of furoic acid derivative of formula (I) obtained at the end of the reaction divided by the number of moles of furfural derivative of formula (II) initially introduced.
  • carbon balance is understood to mean the ratio of the number of carbon atoms present in the reactor at the end of the reaction divided by the number of carbon atoms initially present in the reactor.
  • Another advantage of the present invention is that the operating conditions are simple to implement and allow the direct production of the furoic acid derivative of formula (I) free of any salt, due to the absence of base in the substance. reaction medium.
  • the absence of base in the reaction medium also makes it possible to avoid the degradation of the catalyst support and the leaching of metal particles in the liquid phase, which makes the catalyst recyclable for several successive uses in a closed reactor or stable under flow in a reactor. open.
  • the present invention also relates to a non-alkaline composition comprising at least furfuraldehyde and supported gold nanoparticles.
  • this composition also contains a furfural derivative of formula (II) distinct from furfuraldehyde and, where appropriate, water.
  • the composition is non-alkaline.
  • the gold nanoparticles suitable for the invention are well known and are already commonly used in chemistry as catalysts for reactions of the hydrogenation or oxidation type as well as in particular in optics, electronics, pharmacology, diagnostics or therapy.
  • the nanoparticles are attached to a solid support.
  • the preparation of gold nanoparticles in a mineral confined medium can be carried out in inorganic suspensions (titanium, silica, clay), by reduction of a gold precursor in the presence of a catalyst as described in particular by K. Nakamura et al. (J. Chem. Eng. Jap., 2001, 34, 1538-1544 ).
  • the preparation of gold nanoparticles within a silica matrix bearing hydroxyl groups, by spontaneous reduction of a gold precursor is described by P. Mukherjee et al. (Chem. Mater., 2002, 14, 1678-1684 ), and by T. Yokohama et al. (Journal of Colloid and Interface Science, 2001, 233, 112-116 ).
  • the gold nanoparticles suitable for the invention have a size of between 3 nm and 15 nm, preferably between 5 nm and 10 nm.
  • zirconium dioxide ZrO 2
  • hydrotalcite zirconium dioxide
  • a catalyst suitable for the invention is gold supported on zirconium dioxide or on hydrotalcite.
  • the catalyst used is gold supported on zirconium dioxide.
  • the percentage by weight of gold in the Au / ZrO 2 catalyst for the oxidation of furfuraldehyde is between 1% and 7% by weight, and is preferably equal to 3% by weight, and this in the case of zirconium, used as a support, with a low specific surface, namely less than or equal to 10 m 2 / g.
  • a relatively low percentage by mass of gold makes it possible to disperse the gold on the surface of the ZrO 2 and to increase the quantity of active sites. At higher percentages, the formation of gold aggregates on the surface is possible, which can lead to the formation of a less active catalyst.
  • the furfural / Au molar ratio for the oxidation of furfuraldehyde is between 6 and 34, and preferably this molar ratio is 6.
  • the catalyst used is gold supported on hydrotalcite.
  • the percentage by mass of gold in the Au / hydrotalcite catalyst for the oxidation of furfuraldehyde is between 1% and 3% by weight, and is preferably equal to 2% by weight, and this in the case of hydrotalcite , used as a support, of low specific surface, namely less than or equal to 10 m 2 / g.
  • this percentage of 2% by weight makes it possible to obtain not only a high yield but also a high selectivity for furoic acid.
  • the furfural / Au molar ratio for the oxidation of furfuraldehyde is between 22 and 50, preferably this molar ratio is 22.
  • the supported catalyst according to the invention can be prepared according to any conventional process.
  • a supported catalyst in accordance with the invention can be produced by dissolving a required amount (24.8 mg) of chloroauric acid hydrate (also called tetrachloroauric acid hydrate) in particular sold under the name HAuO 4 by the manufacturer.
  • chloroauric acid hydrate also called tetrachloroauric acid hydrate
  • Alpha Aesar company in an appropriate amount of water (20 mL).
  • Other gold salts can also be used for this type of preparation, such as nitrates, in particular Au (NO 3 ) 3 or chlorides such as in particular AuCl 3 or AU 2 Cl 6 .
  • the solution is subsequently subjected to stirring for a period of between 30 and 60 minutes, preferably for 40 minutes at a temperature of between 25 ° C and 50 ° C, preferably at room temperature (25 ° C) up to in obtaining a precipitate which is filtered and then washed in an appropriate manner.
  • the catalyst is obtained in solid form and then dried in an oven at a temperature between 60 ° C and 100 ° C, preferably at 80 ° C for a period of between 6 and 14 hours, preferably overnight.
  • Example 1 An example of the preparation of a catalyst suitable for the invention is more particularly described in Example 1 below.
  • the oxidation can be carried out in any manner known to those skilled in the art, in particular under oxygen or air pressure, preferably under oxygen pressure.
  • the oxygen or air pressure used is such that the molar ratio O 2 / furfural derivative of formula (II) is greater than 2.
  • the pressure may in particular be 10 to 20 bars (ie 10.10 5 to 20.10 5 Pa) of air, preferably 15 bars (ie 15.10 5 Pa) of air.
  • the partial pressure of oxygen can be 5 to 20 bars (i.e. 5.10 5 to 20.10 5 Pa), preferably 10 to 15 bars (i.e. 10.10 5 to 15.10 5 Pa), more particularly 15 bars (i.e. 15.10 5 Pa) .
  • the reaction temperature for the oxidation of the furfural derivative of formula (II), in particular furfural is between 70 ° C and 150 ° C, in particular between 90 ° C and 120 ° C, and preferably is 110 ° C.
  • a temperature above 120 ° C is not preferred insofar as it is liable to cause the degradation of the furfuraldehyde and / or the product, the formation of various carbon compounds as well as a reduction in the carbon balance of the reaction. .
  • the deposition of carbon on the metal catalysts can cause the deactivation of the catalyst.
  • the reaction time for the oxidation of the furfural derivative of formula (II), in particular furfural is between 1 hour and 15.5 hours, preferably between 2 hours and 4 hours. As detailed in the experimental part below, it was observed that a reaction time longer than 4 hours no longer significantly increases the yield of this reaction and that after a period of 15.5 hours, the furfuraldehyde becomes unstable and the amount of secondary products is no longer negligible.
  • the process can be implemented in continuous or batch mode.
  • the method according to the invention is implemented in batch.
  • the process according to the invention can be applied industrially to the oxidation of furfuraldehyde and its derivatives to obtain the corresponding carboxylic acid free of any salt.
  • chloroauric acid hydrate (Au 49% min, from the company Alpha Aesar, 99.9%) are dissolved in 20 mL of water.
  • the solution is stirred for 40 minutes at room temperature (25 ° C.) until a purple precipitate is obtained.
  • the precipitate thus obtained is then filtered off under vacuum and washed 3 times with water (3 times 20 mL) and 1 time with acetone (20 mL).
  • the solid thus obtained is subsequently dried in an oven at 80 ° C. overnight.
  • chloroauric acid hydrate (Au 49% min, from the company Alpha Aesar, 99.9%) are dissolved in 20 mL of water.
  • 912 mg of hydrotalcite, synthesized in the laboratory with a low specific surface area of 10 m 2 / g are added. The mixture is then stirred at room temperature (25 ° C.) for 10 minutes.
  • the solution is stirred for 40 minutes at room temperature (25 ° C.) until a purple precipitate is obtained.
  • the precipitate thus obtained is then filtered off under vacuum and washed 3 times with water (3 times 20 mL) and 1 time with acetone (20 mL).
  • the solid thus obtained is subsequently dried in an oven at 80 ° C. overnight.
  • the catalytic tests are carried out in a 50 mL autoclave reactor equipped with a thermocouple (Top Industrie Autoclave 2456). The procedure for a standard test is detailed below.
  • the amount is adjusted according to the test to be carried out, for example 50 mg (from 10 to 150 mg) of furfuraldehyde are added to distilled water (10 mL) and left under magnetic stirring for 10 minutes. 9 mL of the furfural solution are then added to the autoclave reactor at atmospheric pressure and at room temperature (25 ° C.).
  • catalysts suitable for the invention which are tested namely Au / ZrO 2 and Au / hydrotalcite, are those prepared according to the protocol of Example 1.
  • reaction time imposed for these tests can also be variable depending on the parameter tested, as specified below, it can be 1 hour, 2 hours, 4 hours, or even 15.5 hours.
  • the reactor is cooled to room temperature (25 ° C) and the resulting solution is taken from the reactor, centrifuged to separate it from the particles of residual solid catalyst and analyzed by HPLC (high performance liquid chromatography), the protocol of which is detailed below.
  • HPLC high performance liquid chromatography
  • the reaction mixture is filtered using an HPLC filter (2.5 microns), then is diluted 5 times with water.
  • the analysis by liquid chromatography is carried out on a Shimadzu UFLC-MS 20-20 HPLC chain equipped with a Phenomenex Synergi 2.5 ⁇ m Hydro-RP 100 ⁇ column. The column is purged at 0.5 mL / min at room temperature (25 ° C) with an aqueous solution of 0.1% trifluoroacetic acid as mobile phase, for 12 minutes. The retention times for each compound are verified using commercial standards. The conversion, the yields and the selectivity are determined by the standard curve method (performed for each compound).
  • reaction rate is calculated as follows: Furfural Tinitial - Furfural Tfinal mmol time min ⁇ mass At mg
  • the oxidation process as described above is carried out with the Au / ZrO 2 catalyst in accordance with the invention as synthesized in example 1a).
  • the percentage by mass of gold in this catalyst is 3% by weight.
  • the O 2 pressure, the stirring speed and the imposed amount of catalyst are those indicated in Example 2.
  • the amount of furfural used is 50 mg, and the reaction time is 1 hour.
  • reaction temperatures tested are 90 ° C, 110 ° C and 120 ° C.
  • a preliminary test, outside the invention, is carried out in the presence of ZrO 2 alone, that is to say without gold nanoparticles. It should be noted that the oxidation reaction of furfuraldehyde does not take place.
  • the oxidation process as described above is carried out with the Au / ZrO 2 catalyst in accordance with the invention.
  • Four different percentages by weight of gold were tested for this catalyst, namely 1%, 3%, 5% and 7% by weight.
  • the catalysts are prepared according to the synthesis protocol described in example 1a), optionally adapted according to the desired weight percentage.
  • the O 2 pressure, the stirring speed and the quantity of catalyst imposed are those indicated in Example 2.
  • the quantity of furfuraldehyde used is 50 mg, the reaction temperature is 110 ° C, and the reaction time. is 4 hours.
  • the oxidation process as described above is carried out with the Au / ZrO 2 catalyst in accordance with the invention as synthesized in example 1a).
  • the percentage by mass of gold in this catalyst is 3% by weight.
  • the O 2 pressure, the stirring speed and the amount of catalyst imposed are those indicated in Example 2.
  • the amount of furfural used is 50 mg, and the reaction temperature is 110 ° C.
  • reaction times tested are 1 hour, 2 hours, 4 hours and 15.5 hours.
  • the oxidation process as described above is implemented with different catalysts based on gold nanoparticles, namely Au / CeO 2 , Au / MgO, Au / hydrotalcite as synthesized in example 1b) and Au / ZrO 2 as synthesized in example 1a).
  • the Au / CeO 2 and Au / MgO catalysts, according to the invention can be prepared by any method known to those skilled in the art and in particular according to those described in example 1 above.
  • the percentage by weight of gold in these catalysts is 2% or 3% by weight, as specified in Table 4 below.
  • the O 2 pressure, the stirring speed and the quantity of catalyst imposed are those indicated in Example 2.
  • the reaction temperature is 110 ° C. and the reaction time is 2 hours.
  • the amount of furfuraldehyde used it is 50 mg.
  • the oxidation process as described above is carried out with the Au / ZrO 2 catalyst in accordance with the invention as synthesized in example 1a).
  • the percentage by mass of gold in this catalyst is 3% by weight.
  • the O 2 pressure, the stirring speed and the quantity of catalyst imposed are those indicated in Example 2.
  • the reaction temperature is 110 ° C. and the reaction time is 4 hours.
  • the amount of furfuraldehyde used it is adjusted in order to obtain three furfuraldehyde / Au molar ratios of 34, 18 and 6 respectively.
  • the oxidation process as described above is carried out with the Au / hydrotalcite catalyst in accordance with the invention as synthesized in example 1b).
  • the percentage by weight of gold in this catalyst is 2% by weight.
  • the O 2 pressure, the stirring speed and the quantity of catalyst imposed are those indicated in Example 2.
  • the reaction temperature is 110 ° C. and the reaction time is 2 hours.
  • the amount of furfuraldehyde used it is adjusted in order to obtain a furfuraldehyde / Au molar ratio of 22.
  • the induced plasma analyzes (ICP) of the reaction solution for the tests (catalytic tests carried out with the 3% Au / ZrO 2 catalyst in accordance with the invention as synthesized in example la) after 1 and 15.5 hours confirmed that no loss of metal residues occurred during the reaction.
  • ICP Optical Emission Spectrometry (ICP-OES) measurements are performed on an Agilent 720-ES spectrometer. Samples are prepared by digestion using aqua regia. The amount of gold in the solution is determined using the calibration curves obtained with standard commercial solutions.
  • Table 7 summarizes the data recorded, in particular the average intensity and RSD intensity (in English: Relative Standard Deviation, coefficient of variation) after 1 hour (blank) and 15.5 hours of reaction (catalytic test) .
  • ⁇ b> ⁇ u> Table 7 ⁇ /u> ⁇ /b> At 211.068 Blank reference (after 1 hour of reaction)
  • Medium intensity 14.286 Intensity% RSD 26,781 Measured after 15.5 hours of reaction

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Claims (22)

  1. Verfahren zur Herstellung von Furonsäure oder von einem Derivat von Formel (I):
    Figure imgb0008
    wobei R1; R2, R3 und R4 unabhängig voneinander ein Wasserstoffatom, eine lineare oder verzweigte C1-C6-Alkylgruppe, eine -C(=O)-H-Gruppe oder eine -COOH-Gruppe darstellen,
    mit der Maßgabe, dass mindestens eine der Gruppen R1, R2, R3 und R4 eine -COOH-Gruppe ist,
    durch heterogene katalytische Oxidation von Furfural oder von einem Derivat von Formel (II):
    Figure imgb0009
    wobei R'1; R'2, R'3 und R'4 unabhängig voneinander ein Wasserstoffatom, eine lineare oder verzweigte C1-C6-Alkylgruppe oder eine -C(=O)-H-Gruppe darstellen,
    mit der Maßgabe, dass mindestens eine der Gruppen R'1, R'2, R'3 und R'4 eine -C(=O)-H-Gruppe ist,
    dadurch gekennzeichnet, dass die Oxidation in Anwesenheit eines Katalysators basierend auf Goldnanopartikeln auf einem Träger und in einem nicht alkalischen wässrigen Medium mit einem pH-Wert von weniger als 8 durchgeführt wird.
  2. Verfahren nach Anspruch 1, wobei R1 und R4 jeweils eine -COOH-Gruppe darstellen und R2 und R3 ein Wasserstoffatom darstellen.
  3. Verfahren nach Anspruch 1, wobei R4 eine -COOH-Gruppe ist und R1; R2 und R3 ein Wasserstoffatom darstellen.
  4. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das nicht-alkalische wässrige Medium mit einem pH-Wert von weniger als 8 einen pH-Wert von höchstens 6 aufweist.
  5. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das wässrige Medium frei von organischen Lösungsmitteln ist.
  6. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das wässrige Medium aus Wasser als Lösungsmittelmedium besteht.
  7. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass es mindestens die Schritte umfasst, die aus Folgendem bestehen:
    (a) Bereitstellen einer nicht-alkalischen wässrigen Lösung, die mindestens ein Furfuralderivat von Formel (II) enthält;
    (b) Inkontaktbringen des Derivats von Formel (II) des Mediums (a) mit gasförmigem Sauerstoff in Anwesenheit von mindestens einer katalytisch wirksamen Menge an Goldnanopartikeln auf einem Träger und unter nicht-alkalischen Bedingungen, die die Oxidation des Furfuralderivats von Formel (II) zu dem Furosäurederivat von Formel (I) begünstigen.
  8. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Oxidation unter einem Sauerstoffpartialdruck zwischen 5,105 Pa und 20,105 Pa, vorzugsweise zwischen 10,105Pa und 15,105Pa, insbesondere gleich 15,105 Pa, durchgeführt wird.
  9. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Oxidation bei einer Temperatur zwischen 70 °C und 150 °C, vorzugsweise zwischen 90 °C und 120 °C, noch bevorzugter 110 °C, durchgeführt wird.
  10. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Katalysator Gold auf Zirkoniumdioxid oder auf Hydrotalcit getragen ist.
  11. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Katalysator Gold auf Hydrotalcit getragen ist.
  12. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Katalysator Gold auf Zirkoniumdioxid getragen ist.
  13. Verfahren nach Anspruch 10 oder 12, dadurch gekennzeichnet, dass der Masseprozentsatz an Gold in dem Au/ZrO2-Katalysator für die Oxidation von Furfural zwischen 1 und 7 Gewichtsprozent, vorzugsweise 3 Gewichtsprozent, liegt.
  14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass das als Träger verwendete Zirkoniumdioxid eine spezifische Oberfläche von 10 m2/g oder weniger besitzt.
  15. Verfahren nach einem der Ansprüche 12 bis 14, dadurch gekennzeichnet, dass das Molverhältnis Furfural/Au für die Oxidation von Furfural zwischen 6 und 34 liegt und vorzugsweise das Verhältnis Furfural/Au 6 ist.
  16. Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass der Masseprozentsatz an Gold in dem Au/Hydrotalcit-Katalysator für die Oxidation von Furfural zwischen 1 und 3 Gewichtsprozent liegt und vorzugsweise 2 Gewichtsprozent ist.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, dass der als Träger verwendete Hydrotalcit eine spezifische Oberfläche von weniger als oder gleich wie 10 m2/g besitzt.
  18. Verfahren nach einem der Ansprüche 11, 16 und 17, dadurch gekennzeichnet, dass das Molverhältnis Furfural/Au für die Oxidation von Furfural zwischen 22 und 50 liegt, und vorzugsweise das Verhältnis Furfural/Au 22 ist.
  19. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Größe der Goldnanopartikel in dem Katalysator für die Oxidation von Furfural zwischen 3 nm und 15 nm liegt und vorzugsweise zwischen 5 nm und 10 nm ist.
  20. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass es in einem kontinuierlichen oder chargenweisen Betrieb durchgeführt werden kann.
  21. Nicht-alkalische Zusammensetzung, umfassend mindestens Furfural und Goldnanopartikel auf einem Träger.
  22. Zusammensetzung nach Anspruch 21, ferner umfassend ferner ein Furfuralderivat von Formel (II), das sich von Furfural unterscheidet, und optional Wasser.
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